1, 3-disubstituted derivatives of 4, 5, 6, 7, 10, 10-hexachloro-4, 7-endomethylene-4, 7, 8, 9-tetrahydrophthalane



United States atent O 1,3-DISUBSTITUTED DERIVATIVES F 4,5,6,7,10,

Germany, assignors to Ruhrchemie Aktiengesellschaft, Oberhausen-Holten, Germany, a corporation of Germany 7 N0 Drawing. Application August 9, 1957 Serial No. 677,235 Claims priority, application Germany August 11, 1956 2 Claims. (Cl. 260-45462) This invention relates to and has as its object the production of 1,3-disubstituted derivatives of 4,5,6,7,10, 10 hexachloro 4,7-endomethylene-4,7,8,9-tetrahydrophthalane which are highly effective insecticides, fungicides and acaricides and which can also be used as intermediate products for further organic synthesis.

The tetrahydrophthalane derivatives in accordance with the invention have the formula: I

in which R is a fluorine atom or a lower alcoholate or acetoxy radical, as for exmaple, the radicals, F, OCH OC H -OC H OCH C'H=CH OCH C=CHOCOCH The starting material for the production of the tetrahydrophthalane derivatives in accordance with the invention is 1,3,4,'5,6,7,10,10-octachloro-4,7-endomethylcue-4,7,8,9-tetrahydrophthalane which is produced in the known manner by chlorinating 4,5,6,7,l0,IO-hexachloro- 4,7-end0methylene-4,7,8,9 tetrahydrophthalane. The chlorination results in the introduction of two new chlorine atoms in the 0c and a position with .respect to the oxygen atom of the phthalane ring system. There- 'activity of the chlorine atoms in the 1 and 3-positions is substantially greater than that of the other chlorine atoms positioned in the 'bicycloheptene ring.

The starting material for the process in accordance with the invention may be obtained, for example, by the methods set forth in Dutch Patent 83,632; in British Patent 772,212.

The tetrahydrophth alane derivatives are formed in accordance with the i'nventionby' reacting 1,3,4,5,6,7,10, 10-octachloro-4,7-endomethylene 4,7,8,9 tetrahydrophthalane with a compound of the formula MeR in which Me is a metal of the first group of periodic system, as for example, sodium, potassium or silver and R is fluorine or lower alcoholate radical or acetoxy radical. The reaction very surprisingly results in the substitution of R for the chlorine atoms in the 1 and 3-positions in a smooth reaction without efiecting the halogen atoms positioned in the bycycloheptene portion of the molecule. The convertion takes place exclusively at the 1 and 3 carbon atoms so that the substitution only occurs at these points on the molecule even if the reaction is effected in an alkaline medium. The reaction proceeds in accordance with the following reaction scheme:

H 01 H R c1 01 n H 01 2MB c1 01 or o 01001 0+2MeCl o1 o1 w/ 04 11 or n a OOOCH 2,879,275 Patented Mar. 24, 1959 '2 r in which Me represents a metal-of the first group oft-he periodic system, as for example, sodium, potassium or silverand R represents a fluorine atom or a lower alcoholate or acetoxy radical as forexample, F, OCH OC H 00 1-1 :OCH CH=CH OCH C=CH,

The reaction may be etfected by contacting the 1,3,4,5, 6,7,10,10 octachloror4, 7-endomethylene 4,7,8,9-tet rahydrophthalane directly with the metal salt or the reaction may be effected in suitable suspending agents or solvents. Suitable solvents include water or lower alco hols while suitable suspending agents include aliphatic, alicyclic or aromatic hydrocarbons or ethers. The reaction proceeds at normal or elevated temperatures and the reaction mixture is processed in theconventional manner and the resulting product is purified by crystallization or distillation which is preferably eflected under vacuum.

The compounds obtained'in accordance with the invention are crystallized materials or highly viscous oils of the yellowish color which have high insecticidal, fungi- 'cidal or acaricidal properties and may also be used as intermediate products for further organic synthesis.

8.2 grams of 1,3,4,5,-6,7,10,10-octachloro-4,7-endomethylene-4,7,8,9-tetrahydrophthalane were dissolved in cc. of acetonitrile andAO grams of 28% silver monofluoride were added to the solution. After heating for 12 hours on a water bath the solution was filtered and the acetonitrile was distilledoif under vacuum. From the residue which was dissolved in ether and treated with activated charcoal there could be separated 3.7 grams of a compound which contained 5.8% of fluorine. By chromatography at a column of A1 0 of 30 cm. in length and 20 mm. diameter using petroleum ether as the eluting egent there was obtained0.8 gram of 1,3difluoro-4,5,6,7, l0,1-O-hexachloro-4,7-endomethylene-4,7,8,9 tetrahydrophthalane which had a (corrected) melting point of 181-182 C.

The unpurified reaction product of l,3,4,5,7,10,10-octachloro-4,7-endomethylene-4,7,8,9 tetrahydrophthalane and silver monofluoride has a surprisingly high insecticidal efficiency as compared with the starting material as may be seen from thefollowing table. Particularly remarkable is thehigh intial efiiciency of the fluorinated products.

Table concentra- Irrevers- Time tion of ibly dam- Insecticide of active aged action substance, animals,

'y/cmfi percent 6. 10 60 1. 37 7 Chlordane g 1. 37 7 0. 685 4 6. 85 5 60 1. 37 5 Aldrin 153g 90 1. 37 17 0.685 10 6. 85 61 1,3,4,5,6,7,10,10-octachloro-4,7-methyl- 60 2; ene-4,7,8,9-tetrahyd.rophthalane. 85 72 90 1. 37 67 unpurified reaction product of g? 3g 1,3,4,5,7,10,10-0ctachloro-4,7-endo- 60 37 90 methylene-4,7,8,Q-tetrahydrophtha- 0 6 73 lane and silver monofluoride i 85 90 l. 37 96 0. 685 86 layer which separated was evaporated under vacuum after drying with annealed. sodium sulfate. 1,3-dimethoxy-4,5,6,7,10,l-hexachloro:4,7 endomethylene- 4,7,8,9-tetrahydrophthalane in a yield of 2,8 grams (69.5% of the theoretically possible amount) was obtained as the residue. pound was 167-168 C. after recrystallization from kerosene.

' EXAMPLE 3 of were dissolved in 50 cc. of anhy-,-

drous ethyl alcohol; and 8.2 grams of 1,3,4,s,6,7,10,10-" octachloro-4,7-endomethylene-4,7,8,9 tetrahydrophthalane were added to this solution in portions. Each addition was accompanied by an instantaneous vigorous reaction. Upon completion of the reactiontthe product:; was poured into water, extracted with ether and, after separation of the ether layer, concentrated by evaporation under vacuum. This resulted in 4.1 grams of 1,3-diethoxy-4,5,6,7,10,10-hexachloro-4,7-endomethylene 4,7,

8,9-tetrahydrophthalane(48% "of the theoretically pos-;

sible quantity). When recrystallized from methanol, the compound first melted at 67 C., but then solidified and thereafter had a melting pointtcorrj of 7T1 C. p

' EXAMPL 1;.

8.2 grams of 1,3,4,5,6,7,10,10-octachloro-ij-endomethylene-4,7,8,9-tetrahydrophthalane were dissolved in 50 cc. of benzene and slowly added dropwise to a solution of 2 grams of sodium in 10 ccof allylalcohol. After heating for 8 hours at 50 Cithe reaction solution, was treated with 100' cc. of water and the benzene layer was concentrated by evaporation under vacuum after drying with sodium sulfate. The residue of 4 grams (44% of the'theory) had a boiling point. (corn) of 130-145 C. at 0.05 mm. Hg and a refractive index,

n of 1.5360, which corresponded to 1,3-dia1lyloxy- 4 ,5,6,7,10,l0-hexachloro-4,7" endomethylene 4,7,13,9-

tet'rahydrophthalane. EXAMPLE 5 The melting point (corrected) of the com- 2.0 grams of l,3,4,5,6,7,10,10-octachloro-4,7-endo-{if methylene-4,733-tetrahydrophthalane and 2.0 grams of silver acetate were dissolved in 500 cc. or wt. percent aqueous acetic acid and heated for 16 'hours with refluxing. Thereafter, the solution was filtered off from the precipitated silver chloride and concentrated by evaporation under vacuum. The residue was dissolved in ether, treated with activated charcoal and again evaporated to dryness. This resulted in 1.2 grams (66% of the theory) of l ,3-diacetoxy'-4, 5,6,7,l0,10-hexachloro-4,7- endomethylene-4J,8,9wtetrahydrophthalane which had a meltin'gpoint (corrected) of 267 C. after recrystallization from gasoline.

' EXAMPLE 6 8.2grams (0.02 mol) of l,3,4,5,6,7,10,10-octachloro- 4,7-methylene-4,7,8,9-tetrahydrophthalane were dissolved in 50 cc. of benzene and to this solution there was slowly added in drops a solution of 2 grams of sodium in 25 cc. of 'propargyl alcohol and 30 cc. of benzene at 20-30 C. After further heating for 8 hours at 50 C. the reaction product wastreated with 50 cc. of water and the benzene layer was concentrated by evaporation under vacuum after drying with sodium sulfate. The residue obtained was distilled under a vacuum of 0.2 mm. Hg and the resulting distillate which had a boilingpoint of 180C. was recrystallized from petroleum ether after crystallization. The 1,3-dipropargyloxy-4,5,6,7,10,10-

'hexachloro-4,7-mcthylene 4,7,8,9 tetrahydrophthalane obtained in a yield of 5 grams(55.4% of the theory) had a melting point of 71 C.

We claim: p 1. A tetrahydrophthalane derivative having the formula: i

in which the Rs are the same member selected from the. group consisting of OCH OC H OC;,H-,, 0CH CH='CH OCH CECH and OCOC-H radicals.

- 2; Process for the production of 1,3-disubstituted derivatives of 4,5 ,6,7,1 0, lO-hexachloro-4,7 endomethylene- 4,7,8,9-tetrahydrophthalane which I comprises reacting 1,3,4,5,6,7,10,10-octachloro-4,7-endomethy1ene 4,7,8,9-

tetrahydrophthalane with a compound having the formula MeR in which Me is a member selected from the group consisting of potassium, sodium and silver, and R is a member'selected from the group consisting of 0CH OC H jOC H OCH CI-I=CH;,, OCHZCEOH and OCOCHQ radicals and recovering the 1,3-disubstituted derivative formed.

No references cited. 

1. A TETRAHYDROPHTHALANE DERIVATIVE HAVING THE FORMULA: 